US9416095B2 - Salts, crystals, complexes, and derivatives of threonine diacetic acid, a process to prepare threonine diacetic acid, and the use thereof - Google Patents

Salts, crystals, complexes, and derivatives of threonine diacetic acid, a process to prepare threonine diacetic acid, and the use thereof Download PDF

Info

Publication number
US9416095B2
US9416095B2 US14/905,432 US201414905432A US9416095B2 US 9416095 B2 US9416095 B2 US 9416095B2 US 201414905432 A US201414905432 A US 201414905432A US 9416095 B2 US9416095 B2 US 9416095B2
Authority
US
United States
Prior art keywords
threonine
salt
diacetic acid
acid
sodium
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
US14/905,432
Other versions
US20160159730A1 (en
Inventor
Axel Carstens
Tjerk Oedse Boonstra
Alexey Borisovich ZAITSEV
Martin Heus
Wouter Jan VEENIS
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nouryon Chemicals International BV
Original Assignee
Akzo Nobel Chemicals International BV
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Akzo Nobel Chemicals International BV filed Critical Akzo Nobel Chemicals International BV
Assigned to AKZO NOBEL CHEMICALS INTERNATIONAL B.V. reassignment AKZO NOBEL CHEMICALS INTERNATIONAL B.V. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: HEUS, MARTIN, VEENIS, Wouter Jan, BOONSTRA, TJERK OEDSE, CARSTENS, AXEL, ZAITSEV, Alexey Borisovich
Publication of US20160159730A1 publication Critical patent/US20160159730A1/en
Application granted granted Critical
Publication of US9416095B2 publication Critical patent/US9416095B2/en
Assigned to WILMINGTON TRUST (LONDON) LIMITED, AS COLLATERAL AGENT reassignment WILMINGTON TRUST (LONDON) LIMITED, AS COLLATERAL AGENT SECURITY INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: AKZO NOBEL CHEMICALS B.V., AKZO NOBEL CHEMICALS INTERNATIONAL B.V., AKZO NOBEL SURFACE CHEMISTRY LLC, STARFRUIT US MERGER SUB 1 LLC, STARFRUIT US MERGER SUB 2 LLC
Assigned to NOURYON CHEMICALS INTERNATIONAL B.V. reassignment NOURYON CHEMICALS INTERNATIONAL B.V. CHANGE OF NAME (SEE DOCUMENT FOR DETAILS). Assignors: AKZO NOBEL CHEMICALS INTERNATIONAL B.V.
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
    • C07C227/14—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof
    • C07C227/18—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof by reactions involving amino or carboxyl groups, e.g. hydrolysis of esters or amides, by formation of halides, salts or esters
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
    • C07C227/14—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof
    • C07C227/16—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof by reactions not involving the amino or carboxyl groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
    • C07C229/02—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton
    • C07C229/04—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
    • C07C229/06—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton
    • C07C229/10—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton the nitrogen atom of the amino group being further bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
    • C07C229/16—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton the nitrogen atom of the amino group being further bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings to carbon atoms of hydrocarbon radicals substituted by amino or carboxyl groups, e.g. ethylenediamine-tetra-acetic acid, iminodiacetic acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
    • C07C229/76—Metal complexes of amino carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
    • C07C255/24—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms containing cyano groups and singly-bound nitrogen atoms, not being further bound to other hetero atoms, bound to the same saturated acyclic carbon skeleton
    • C07C255/25—Aminoacetonitriles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D265/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one oxygen atom as the only ring hetero atoms
    • C07D265/28—1,4-Oxazines; Hydrogenated 1,4-oxazines
    • C07D265/30—1,4-Oxazines; Hydrogenated 1,4-oxazines not condensed with other rings
    • C07D265/32—1,4-Oxazines; Hydrogenated 1,4-oxazines not condensed with other rings with oxygen atoms directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/33—Amino carboxylic acids

Definitions

  • the present invention relates to new salts, crystals, complexes, and derivatives of the chelating agent threonine-N,N-diacetic acid, to processes to prepare such threonine diacetic acid and its salts, complexes, crystals, and derivatives, and to the use thereof.
  • the detergent market is currently undergoing important changes. Due to ecological and regulatory reasons the use of phosphate in high concentrations in detergent formulations is to be banned altogether or must at least be greatly reduced.
  • the formulators of detergent products have to find alternatives to replace the phosphate compounds, with the most promising replacements being biodegradable chelating agents. In other areas where acids are used, there is a growing trend towards replacing acids with more eco-friendly materials. In the oil industry operators are also looking for alternatives, and here again biodegradable chelating agents that can be isolated in their acidic form proved to be promising alternatives.
  • chelating agent is serine-N,N-diacetic acid.
  • U.S. Pat. No. 5,019,296 discloses the use thereof in detergents as complexing agent, bleaching agent stabilizer and builder.
  • the chelating agent should be obtainable in good yield by a simple process with little or no colour.
  • U.S. Pat. No. 5,019,296 discloses a preparation of serine-N,N-diacetic acid by reacting formaldehyde and hydrogen cyanide with serine and S Korman et al., Journal of Biological Chemistry, Vol. 22, no. 18, 1 Jan. 1956, pp. 113-132 discloses a preparation of serine diacetic acid by reacting serine with monobromo acetic acid, which is from an industrial perspective a less attractive route because of lower yields and expensive raw materials.
  • the present invention now provides processes to prepare threonine N,N-diacetic acid and salts or complexes thereof, provides salts of threonine N,N-diacetic acid of the formula CH 3 —CHOH—C(H)(COOM)-N—(CH 2 —COOM) 2 , wherein at least one M is sodium, potassium, lithium, cesium, ammonium, and provides complexes of threonine diacetic acid and a divalent or trivalent cation, wherein the cation is selected from the group of calcium, magnesium, iron, zinc, manganese, aluminum, copper, and cobalt.
  • the present invention covers each of the above products in which the amount of the L-enantiomer (i.e. the 2S, 3R threonine enantiomer; the natural amino acid based enantiomer) is at least 50 mole %, as well as crystals of any of the above products and liquids containing one or more of the above products and a solvent, and dispersions thereof containing a continuous liquid phase.
  • the amount of the L-enantiomer i.e. the 2S, 3R threonine enantiomer; the natural amino acid based enantiomer
  • threonine-N,N-diacetic acid is mentioned together with for example the above discussed serine-N,N-diacetic acid, which is, as said, a chelating agent having a not too different chemical structure.
  • the present invention provides processes to prepare threonine N,N-diacetic acid.
  • the processes of the invention do give the much less coloured to non-coloured chelating agent threonine N,N-diacetic acid and salts thereof, from which also low coloured complexes can be prepared, though it should be realized that some complexes are intrinsically coloured due to the choice of cation, e.g. iron, copper, manganese and cobalt complexes are oftentimes coloured.
  • the processes of the invention to prepare threonine N,N-diacetic acid are a process comprising two or more steps wherein in one step threonine, a sodium or potassium salt thereof or a mixture thereof is reacted with formaldehyde and hydrogen cyanide, at a pH equal to or below 7, and in another step the nitrile compound formed in the first step is hydrolyzed in the presence of a base, or less preferably in the presence of an acid (a Singer process); a process comprising reacting threonine, a sodium or potassium salt thereof or a mixture thereof with formaldehyde, hydrogen cyanide, a potassium or sodium salt thereof or a mixture thereof, and potassium hydroxide, sodium hydroxide or a mixture thereof, in an aqueous solution, at a pH higher than 7 and at an elevated temperature to remove formed NH 3 (a Strecker/Bersworth process); and a process wherein threonine is reacted with a monohaloacetic acid (CH2X—CO
  • the invention in addition relates to the molecule 4-(carboxymethyl)-2-methyl-6-oxomorpholine-3-carboxylic acid, which is basically the molecule of threonine N,N-diacetic acid having undergone a ring closure reaction.
  • This ring closure takes place after subjecting threonine-N,N-diacetic acid to conditions under which water is easily extracted, which are often acidic conditions, such as adding an acid, an ion exchange resin or subjecting the molecule to acidifying electrodialysis, but also increasing the temperature or reducing the pressure, as represented in the scheme below.
  • threonine-N,N-diacetic acid is capable of ring closing as indicated above makes it a chelating agent with delayed functionality, which is an advantage in many applications where the chelating capacity should take place slowly and not instantaneously, such as the use of the compound in the oil or gas field. It should be noted that threonine N,N-diacetic acid much easier and more completely undergoes the ring closure than serine-N,N-diacetic acid, which is the most similar molecule from a chemical structure perspective, which is another benefit for the products of the present invention.
  • threonine-N,N-diacetic acid can be produced in high yields, forms relatively stable complexes with many cations (to phrase it differently, it is one of the stronger chelating agents within the group of chelating agents that do not bind cations so strongly that they will hardly release them again). Further, the compound is readily biodegradable.
  • THDA threonine-N,N-diacetic acid
  • alkali metal salts wherein y is more than 1 strike a good balance between low viscosity and being obtainable by a process using raw materials that are easily available on an industrial site for a low price. Also, these alkali metal salts have a reasonable molecular weight to viscosity balance, i.e. they have a sufficiently low viscosity to make them transportable and a sufficiently low molecular weight to get sufficient chelate activity per weight unit of alkalimetal chelate salt.
  • mixed salts of THDA have the benefit that they can be transported in high concentrations (60% expressed in wt % is no problem) while still having a sufficiently low viscosity to be pumpable at low temperatures ( ⁇ 40° C.). This also means that a smaller amount of material needs to be transported to get the same amount of chelate at the place of destination.
  • the mixed salt is lower than for a full potassium version for solutions having the same chelating power.
  • the molecular weight of the trisodium salt of THDA being 301.1, would become 349.5 for the tripotassium salt. So, to get the same active ingredient with respect to sequestering power almost 20% more material would need to be dissolved.
  • the monopotassium disodium THDA of the invention requires only 5% more product to be dissolved instead of 20%, and this without the product having the negative effect of high viscosity at more concentrated solutions when compared with the trisodium version.
  • x is between 1.5 and 2.5 and y is between 0.5 and 1.5, most preferably x is about 2 and y is about 1.
  • the invention provides a process to prepare the above (alkali metal salts of) threonine-N,N-diacetic acid (THDA) comprising reacting threonine, a sodium or potassium salt thereof or a mixture thereof, with formaldehyde, hydrogen cyanide, a potassium or sodium salt thereof or a mixture thereof, and potassium hydroxide, sodium hydroxide or a mixture thereof, in an aqueous solution at an elevated temperature to remove formed NH 3 .
  • THDA threonine-N,N-diacetic acid
  • the molar ratio of sodium to potassium in the reactants is between 1:1 and 5:1.
  • the molar ratio of sodium to potassium in the reactants is between 1:1 and 3:1, most preferably about 2:1.
  • the novel threonine-N,N-diacetic acid salt is prepared by a so-called Strecker/Bersworth route at alkaline conditions using an 1-pot synthesis.
  • the reaction route encompasses reacting threonine with formaldehyde and hydrogen cyanide in the presence of sodium hydroxide and potassium hydroxide.
  • the excess cyanide/formaldehyde needed is 10% or more; use is made of a minimum of 2.2 equivalents cyanide/formaldehyde per equivalent of threonine.
  • glycolonitrile HO—CH 2 —CN
  • This glycolonitrile is reacted with threonine or the sodium or potassium salt thereof in an alkaline environment (Strecker/Bersworth process). 1 threonine+2HO—CH 2 —CN+3MOH ⁇ THDA-M 3 +2NH 3 +2H 2 O
  • the threonine diacetic acid and its (alkali metal) salts of the invention are prepared by a Singer process comprising two or more steps, wherein in a first step threonine, a sodium or potassium salt thereof or a mixture thereof is reacted with formaldehyde and hydrogen cyanide at a pH equal to or below 7, and in a subsequent step the nitrile compound formed in the first step is hydrolyzed with an alkali metal hydroxide, and optionally acidified in a next step.
  • the acidification step can be performed by adding an organic or inorganic acid, but is preferably done, mainly to avoid the formation of salt, by reaction with an ion exchange resin or by an electrodialytical acidification, such as for example disclosed in EP-A-1004571 or EP-A-2086923.
  • a mixture of alkali metal hydroxides can be used, for example one wherein the molar ratio of sodium to potassium in the reactants is between 1:1 and 5:1.
  • a two-step process in which the first step takes place at neutral or acidic pH (the above so-called Singer process), between 1.6 and 2.4 equivalents of formaldehyde are used per equivalent of threonine or salt thereof and 1.6 to 2.4 equivalents of HCN are used per equivalent of threonine or salt thereof.
  • 1.9-2.1 equivalents of formaldehyde and HCN are used per equivalent of threonine or salt thereof.
  • the amount of formaldehyde and HCN is about 2.0 equivalents per equivalent of threonine or salt thereof.
  • the amount of HCN may be (but does not need to be) the same as the amount of formaldehyde.
  • the first step is split up into two substeps, firstly a reaction of threonine or its salt with formaldehyde to generate a Schiff base intermediate and subsequently a reaction with HCN and remaining formaldehyde to form threonine N,N diacetonitrile.
  • the raw material is monosodium salt of threonine, threonine or the monopotassium salt of threonine.
  • the solubility of threonine can be enhanced by dissolving it in MOH (resulting in the formation of monosodium or monopotassium salt); having about 0.6-1.4 equivalents of base is preferred.
  • the monosodium salt or monopotassium salt of threonine is then dissolved in water and formaldehyde and cyanide are added to obtain final reaction mixture with acidic or neutral pH.
  • the addition of formaldehyde and hydrogen cyanide preferably takes place at a temperature between 0 and 70° C., preferably 0 and 40° C.
  • the result is an intermediate product having two nitrile functionalities.
  • These types of products are known as aminoacetonitriles or, for short, “nitriles”.
  • the nitrile of THDA e.g. threonine-N,N-diacetonitrile, is also indicated as THDN below.
  • the nitrile, being a water-soluble compound, is hydrolyzed in a second step applying caustic.
  • each M and M′ may be the same or different and represent an alkali metal ion.
  • the process has as an additional benefit that having potassium THDN one needs only sodium hydroxide to produce the THDA-KNa2. Not all production locations have access to KOH or storage tanks of KOH; NaOH is more commonly used. Production of a mixed salt is easier than of the full potassium version that requires KOH to be present in each location, i.e. the location carrying out the nitrile hydrolysis only needs the commonly used NaOH.
  • threonine diacetonitrile monopotassium salt is formed by reacting either potassium salt of threonine with hydrogen cyanide and formaldehyde or threonine with potassium cyanide and formaldehyde, the nitrile being hydrolyzed with sodium hydroxide in the subsequent step.
  • threonine As starting material instead of threonine also the potassium salt thereof can be employed.
  • the main advantage of monopotassium salt of threonine in the production process is its very high solubility even at room temperature.
  • Monosodium threonine has a high solubility in water at room temperature (higher solubility compared to the non-salt threonine itself), monopotassium threonine has an even higher solubility.
  • the more concentrated the threonine can be processed the less water removal is required to make a concentrated THDA solution.
  • the final nitrile concentration will be higher due to the higher solubility of potassium salt of threonine. It allows for more economical transport, more output per reactor volume, lower energy costs, and is an easy way to produce highly concentrated final THDA solutions in the hydrolysis of the nitrile functionalities without water removal.
  • the invention provides the following two alternative processes. Firstly, a process comprising titrating threonine-N,N-diacetic acid (or an appropriate derivative or salt thereof) with a sodium salt and a potassium salt wherein the molar ratio of sodium to potassium in the materials is between 5:1 and 1:1 and, secondly, a process of mixing the trisodium salt of THDA and the tripotassium salt of THDA in a molar ratio of between 5:1 and 1:1.
  • the complexes of the present invention are made by contacting a salt of threonine diacetic acid or the acidic version of threonine diacetic acid with a compound containing a divalent or trivalent metal cation, like a salt of such a metal cation, preferably, the carbonate, oxide or hydroxide salt of such cation to avoid the formation of further salts, even more preferably the oxide salt, as hydroxide salts sometimes are not too soluble and the use of carbonate salts may result in the formation of a considerable amount of CO 2 gas, which is sometimes undesirable.
  • a metal oxide it is preferred to use the threonine N—N-diacetic acid in the acidic version.
  • the complexes are normally made in a solvent, preferably water.
  • ammonium salts of the present invention are preferably made by contacting the acidic version of threonine diacetic acid (i.e. wherein at least one of the counterions is a hydrogen ion) with an ammonium salt or ammonia, preferably with NH 4 OH.
  • the present invention relates to the use of the alkali metal salts in a detergent or bleaching composition, a descaling composition, a microbial composition, human food or animal feed composition, an oil or gas well treatment composition, a micronutrient composition, in gas sweetening, pulp and paper bleaching, drilling, or in the preparation of any of such compositions.
  • a 1 liter reactor was charged with 178.5 g threonine, (1.5 moles), 300 g water, and 130 g 50 wt % aqueous NaOH (1.6 moles). The reactor contents were heated to boiling temperature. Simultaneously in circa 3 hours 4.0 moles sodium cyanide solution (30 wt %) and 4.0 moles formaldehyde solution (44 wt %) were dosed. After the dosing was completed 2 hrs of boiling off ammonia/water took place (level control of the mixture by addition of water).
  • Circa 995 grams of a light-coloured solution having a Fe-sequestering capacity of 48 wt % were obtained, which contained ⁇ 1 wt % of the starting material, threonine, indicating a good conversion.
  • a 1 liter reactor equipped with a stirrer, thermometer, and pH meter was charged with 104 g threonine (0.87 moles), 500 g water, and 5.5 grams 50 wt % aqueous NaOH. To this solution 67 g 44.3% formaldehyde solution (0.99 moles) were added. Subsequently over a period of 80 minutes, 54 g HCN (2.00) moles and 67 g (0.99 moles) 44.3 wt % formaldehyde were co-dosed. The pH was adjusted to 4 with 50% sodium hydroxide. The threonine diacetonitrile solution was dosed over a period of 90 minutes to a reactor that contained 209 g 50% caustic and 250 g water. After dosing had been completed the ammonia was boiled off by evaporating water/ammonia at 109° C. using level control by addition of water. The reactor mixture (650 grams) showed a Fe-sequestering capacity of 28%.
  • a 3 liter jacketed reactor with baffles and turbine stirrer was charged with 858 g of water and 361.0 g (3 moles) of L-threonine (99%, Fluka). This slurry is heated to 60° C. The dosing of 50 wt % aqueous NaOH solution was started and the pH value was maintained at 8.0 during the process when dosing a 42.9 wt % aqueous solution of sodium monochloroacetate. The reaction was monitored by the determination of its sequestering value.
  • the solution obtained in example 1 was acidified using an ion exchange resin. Acidification took place using Amberlite IR-120, a strong acid ion exchange resin: 55 g of GLDA solution, 110 g of Amberlite IR-120 as such, and ca 100 g of water were stirred in a 500 ml round-bottomed flask for at least 48 h. After filtering off the resin the solution was dried by evaporation of water at reduced pressure at 70° C. The light-coloured crispy foam obtained was further dried in a vacuum oven at 65° C. This resulted in a solid product in a yield of circa 85%.
  • the ratio of open/closed structure in solution is dependent on a number of factors such as e.g. pH-value, concentration.
  • the ratio of open/closed structure in solid form strongly depends on factors like e.g. drying time, temperature, strength of vacuum applied.
  • Example 2 Water was removed from 50.8 g of the solution of Example 1 using a rotavap at 65° C. under reduced pressure. This resulted in 39.41 g of solid material. After dissolving this solid in glacial acetic acid (100 ml) the solution was precipitated by mixing with about 1,200 ml of isopropyl alcohol (IPA). After filtration through a G2 filter frit the solid was dried in a vacuum oven under reduced pressure at 100° C., resulting in 15.49 g of colourless material with a THDA:THDA ring closed ratio of 80:20
  • IPA isopropyl alcohol
  • Example 1 The solution obtained in Example 1 was used to prepare the powder of threonine diacetate.
  • To the obtained mixture an equimolar amount of an aqueous solution of CaCl 2 .2H 2 O was added, followed by partial evaporation under vacuum to give a concentrated mixture.
  • the concentrated mixture was left standing overnight at room temperature for further crystallization.
  • the obtained solids were filtered off, washed with water (3 ⁇ 1 ml), and dried under vacuum (50° C.) to obtain white crystals.
  • the formation of the crystalline Ca-THDA complex was supported by XRD, ICP, ESI-MS, and NMR analysis of the isolated material.
  • Example 2 Following the procedure as in Example 1, a 1 liter reactor was charged with 157.6 g serine, (1.5 moles), 120 g water, and 123 g 50 wt % aqueous NaOH (1.54 moles). The reactor contents were heated to boiling temperature. Simultaneously in circa 3 hours 4.0 moles sodium cyanide solution (30 wt %) and 4.0 moles formaldehyde solution (44 wt %) were dosed. After the dosing was completed 2 hrs of boiling off ammonia/water took place (level control of the mixture by addition of water). Ca.
  • a 30% aqueous solution of disodium threonine diacetate (129 mg) was mixed well with a DMSO-d 6 /TFA solution (2761 mg, 80:20 w/w) and changes in the obtained mixture were monitored by 1 H NMR at ambient temperature. The steady state was reached after 40 minutes with a conversion of 90% of THDA to cyclic-THDA.
  • THDA can be used in applications that relate to dissolving carbonate or sequestering iron, such as use in the oil field (e.g. dissolving CaCO 3 and controlling iron in subterranean treatment), use in a feed, food or micronutrient composition (e.g. complexing iron and calcium for delivery to growing substrates), use in detergents and water treatments (e.g. sequestering calcium from water to soften water and sequestering iron present in stains), and many more uses.
  • oil field e.g. dissolving CaCO 3 and controlling iron in subterranean treatment
  • use in a feed, food or micronutrient composition e.g. complexing iron and calcium for delivery to growing substrates
  • use in detergents and water treatments e.g. sequestering calcium from water to soften water and sequestering iron present in stains

Abstract

The present invention relates to new salts, complexes, crystals, solutions, dispersions, and slurries of threonine-N,N-diacetic acid or derivatives thereof, to formulations containing those, to processes to prepare those, and to the use thereof.

Description

This application is a national stage filing under 35 U.S.C. §371 of PCT/EP2014/064894, filed Jul. 11, 2014, which claims priority to European Patent Application No. 13176649.5, filed Jul. 16, 2013, the contents of which are each incorporated herein by reference in their entireties.
The present invention relates to new salts, crystals, complexes, and derivatives of the chelating agent threonine-N,N-diacetic acid, to processes to prepare such threonine diacetic acid and its salts, complexes, crystals, and derivatives, and to the use thereof.
The detergent market is currently undergoing important changes. Due to ecological and regulatory reasons the use of phosphate in high concentrations in detergent formulations is to be banned altogether or must at least be greatly reduced. The formulators of detergent products have to find alternatives to replace the phosphate compounds, with the most promising replacements being biodegradable chelating agents. In other areas where acids are used, there is a growing trend towards replacing acids with more eco-friendly materials. In the oil industry operators are also looking for alternatives, and here again biodegradable chelating agents that can be isolated in their acidic form proved to be promising alternatives.
There is a continuous search for new biodegradable chelating agents that are easy to prepare and can be used in the several applications for which chelating agents are used.
One useful, readily biodegradable, chelating agent is serine-N,N-diacetic acid. U.S. Pat. No. 5,019,296 discloses the use thereof in detergents as complexing agent, bleaching agent stabilizer and builder. However, for a chelating agent to be suitable for incorporation in a detergent formulation, the chelating agent should be obtainable in good yield by a simple process with little or no colour.
U.S. Pat. No. 5,019,296 discloses a preparation of serine-N,N-diacetic acid by reacting formaldehyde and hydrogen cyanide with serine and S Korman et al., Journal of Biological Chemistry, Vol. 22, no. 18, 1 Jan. 1956, pp. 113-132 discloses a preparation of serine diacetic acid by reacting serine with monobromo acetic acid, which is from an industrial perspective a less attractive route because of lower yields and expensive raw materials.
When following the process as disclosed in the state of the art, such as the above U.S. Pat. No. 5,019,296 reference, serine-N,N-diacetic acid could only be obtained with a red to brown, sometimes almost black, colour. Such coloured products are highly undesirable, for example when they are used in detergents or in bleaching.
Hence, there is a need in the art to provide alternatives to serine-N,N-diacetic acid or alternative processes that give chelating agents with similar properties but that do not give the same undesired colour, or that do not need additional treatments to remove the colour from the chelating agent.
The present invention now provides processes to prepare threonine N,N-diacetic acid and salts or complexes thereof, provides salts of threonine N,N-diacetic acid of the formula CH3—CHOH—C(H)(COOM)-N—(CH2—COOM)2, wherein at least one M is sodium, potassium, lithium, cesium, ammonium, and provides complexes of threonine diacetic acid and a divalent or trivalent cation, wherein the cation is selected from the group of calcium, magnesium, iron, zinc, manganese, aluminum, copper, and cobalt.
Moreover, the present invention covers each of the above products in which the amount of the L-enantiomer (i.e. the 2S, 3R threonine enantiomer; the natural amino acid based enantiomer) is at least 50 mole %, as well as crystals of any of the above products and liquids containing one or more of the above products and a solvent, and dispersions thereof containing a continuous liquid phase.
It should be noted that a number of documents, for instance JP 11021584, JP 2004204055 and WO 2011/154875, mention the compound threonine diacetic acid. However, none of these documents enables the compound in the sense that they clearly and unambiguously demonstrate how to make such compound or where it was acquired. Hence, there is no indication in these documents that the proprietors really had access to the molecule or any derivative thereof that was obtained in the light of the present invention. And what is more, none of the above documents discloses the salts, derivatives, complexes, liquids, solutions or dispersions of threonine diacetic acid or any of its derivatives or their production process or characteristics. In WO 2011/154875 threonine-N,N-diacetic acid is mentioned together with for example the above discussed serine-N,N-diacetic acid, which is, as said, a chelating agent having a not too different chemical structure.
As indicated above, the present invention provides processes to prepare threonine N,N-diacetic acid. The processes of the invention do give the much less coloured to non-coloured chelating agent threonine N,N-diacetic acid and salts thereof, from which also low coloured complexes can be prepared, though it should be realized that some complexes are intrinsically coloured due to the choice of cation, e.g. iron, copper, manganese and cobalt complexes are oftentimes coloured.
The processes of the invention to prepare threonine N,N-diacetic acid are a process comprising two or more steps wherein in one step threonine, a sodium or potassium salt thereof or a mixture thereof is reacted with formaldehyde and hydrogen cyanide, at a pH equal to or below 7, and in another step the nitrile compound formed in the first step is hydrolyzed in the presence of a base, or less preferably in the presence of an acid (a Singer process); a process comprising reacting threonine, a sodium or potassium salt thereof or a mixture thereof with formaldehyde, hydrogen cyanide, a potassium or sodium salt thereof or a mixture thereof, and potassium hydroxide, sodium hydroxide or a mixture thereof, in an aqueous solution, at a pH higher than 7 and at an elevated temperature to remove formed NH3 (a Strecker/Bersworth process); and a process wherein threonine is reacted with a monohaloacetic acid (CH2X—COOH, X is a halogen atom, such as chlorine, bromine or iodine) at a temperature between 20 and 80° C., and an alkaline pH to liberate formed HX, giving a threonine-N,N-diacetate salt that may optionally be acidified.
Hence, even though there are similarities between the processes of the state of the art to prepare serine-N,N-diacetic acid and those of the present invention to prepare threonine N,N-diacetic acid, quite unexpectedly the processes of the present invention gave low coloured to non-coloured chelating agent products without performing any colour treatment steps.
The invention in addition relates to the molecule 4-(carboxymethyl)-2-methyl-6-oxomorpholine-3-carboxylic acid, which is basically the molecule of threonine N,N-diacetic acid having undergone a ring closure reaction. This ring closure takes place after subjecting threonine-N,N-diacetic acid to conditions under which water is easily extracted, which are often acidic conditions, such as adding an acid, an ion exchange resin or subjecting the molecule to acidifying electrodialysis, but also increasing the temperature or reducing the pressure, as represented in the scheme below.
Figure US09416095-20160816-C00001
The Formation of Cyclic Ester of THDA Upon Acidification
The fact that threonine-N,N-diacetic acid is capable of ring closing as indicated above makes it a chelating agent with delayed functionality, which is an advantage in many applications where the chelating capacity should take place slowly and not instantaneously, such as the use of the compound in the oil or gas field. It should be noted that threonine N,N-diacetic acid much easier and more completely undergoes the ring closure than serine-N,N-diacetic acid, which is the most similar molecule from a chemical structure perspective, which is another benefit for the products of the present invention.
Moreover, threonine-N,N-diacetic acid can be produced in high yields, forms relatively stable complexes with many cations (to phrase it differently, it is one of the stronger chelating agents within the group of chelating agents that do not bind cations so strongly that they will hardly release them again). Further, the compound is readily biodegradable.
The salts of the invention also cover alkali metal salt of threonine-N,N-diacetic acid (THDA) of the formula NaxKyHzTHDA, wherein x and y are more than 0, z is more than and including 0, x and y are up to and including 3, z is lower than 3, and x+y+z=3.
The alkali metal salts wherein y is more than 1 strike a good balance between low viscosity and being obtainable by a process using raw materials that are easily available on an industrial site for a low price. Also, these alkali metal salts have a reasonable molecular weight to viscosity balance, i.e. they have a sufficiently low viscosity to make them transportable and a sufficiently low molecular weight to get sufficient chelate activity per weight unit of alkalimetal chelate salt.
Compared to the full acid of THDA or the trisodium salt of THDA, mixed salts of THDA have the benefit that they can be transported in high concentrations (60% expressed in wt % is no problem) while still having a sufficiently low viscosity to be pumpable at low temperatures (<40° C.). This also means that a smaller amount of material needs to be transported to get the same amount of chelate at the place of destination.
Other advantages of the mixed salt are that the solids content of a mixed THDA salt solution is lower than for a full potassium version for solutions having the same chelating power. The molecular weight of the trisodium salt of THDA, being 301.1, would become 349.5 for the tripotassium salt. So, to get the same active ingredient with respect to sequestering power almost 20% more material would need to be dissolved. The monopotassium disodium THDA of the invention requires only 5% more product to be dissolved instead of 20%, and this without the product having the negative effect of high viscosity at more concentrated solutions when compared with the trisodium version.
Preferably, in the alkali metal salt of THDA of the invention x is between 1.5 and 2.5 and y is between 0.5 and 1.5, most preferably x is about 2 and y is about 1.
In one embodiment the invention provides a process to prepare the above (alkali metal salts of) threonine-N,N-diacetic acid (THDA) comprising reacting threonine, a sodium or potassium salt thereof or a mixture thereof, with formaldehyde, hydrogen cyanide, a potassium or sodium salt thereof or a mixture thereof, and potassium hydroxide, sodium hydroxide or a mixture thereof, in an aqueous solution at an elevated temperature to remove formed NH3.
In an embodiment during the process the molar ratio of sodium to potassium in the reactants is between 1:1 and 5:1. Preferably, the molar ratio of sodium to potassium in the reactants is between 1:1 and 3:1, most preferably about 2:1.
In this embodiment the novel threonine-N,N-diacetic acid salt is prepared by a so-called Strecker/Bersworth route at alkaline conditions using an 1-pot synthesis. The reaction route encompasses reacting threonine with formaldehyde and hydrogen cyanide in the presence of sodium hydroxide and potassium hydroxide. The excess cyanide/formaldehyde needed is 10% or more; use is made of a minimum of 2.2 equivalents cyanide/formaldehyde per equivalent of threonine.
The individual dosing of formaldehyde and HCN can also be combined to generate glycolonitrile (HO—CH2—CN). This glycolonitrile is reacted with threonine or the sodium or potassium salt thereof in an alkaline environment (Strecker/Bersworth process).
1 threonine+2HO—CH2—CN+3MOH→THDA-M3+2NH3+2H2O
Preferably, the threonine diacetic acid and its (alkali metal) salts of the invention are prepared by a Singer process comprising two or more steps, wherein in a first step threonine, a sodium or potassium salt thereof or a mixture thereof is reacted with formaldehyde and hydrogen cyanide at a pH equal to or below 7, and in a subsequent step the nitrile compound formed in the first step is hydrolyzed with an alkali metal hydroxide, and optionally acidified in a next step.
The acidification step can be performed by adding an organic or inorganic acid, but is preferably done, mainly to avoid the formation of salt, by reaction with an ion exchange resin or by an electrodialytical acidification, such as for example disclosed in EP-A-1004571 or EP-A-2086923.
In a preferred embodiment a mixture of alkali metal hydroxides can be used, for example one wherein the molar ratio of sodium to potassium in the reactants is between 1:1 and 5:1.
In a more preferred embodiment, a two-step process in which the first step takes place at neutral or acidic pH (the above so-called Singer process), between 1.6 and 2.4 equivalents of formaldehyde are used per equivalent of threonine or salt thereof and 1.6 to 2.4 equivalents of HCN are used per equivalent of threonine or salt thereof. In an even more preferred embodiment, 1.9-2.1 equivalents of formaldehyde and HCN are used per equivalent of threonine or salt thereof. Most preferably, the amount of formaldehyde and HCN is about 2.0 equivalents per equivalent of threonine or salt thereof. In the process the amount of HCN may be (but does not need to be) the same as the amount of formaldehyde.
For very low NTA levels the two-step Singer process is preferred over the Strecker process.
The overall reaction is:
1 threonine+2CH2O+2HCN+3MOH→THDA-M3+2NH3+H2O
It will be clear that instead of starting with threonine, it is possible to use the sodium or potassium salt of threonine. The same holds for hydrogen cyanide; sodium cyanide and potassium cyanide are alternatives. Potassium hydroxide can be used instead of sodium hydroxide.
In a more preferred embodiment, the first step is split up into two substeps, firstly a reaction of threonine or its salt with formaldehyde to generate a Schiff base intermediate and subsequently a reaction with HCN and remaining formaldehyde to form threonine N,N diacetonitrile.
In the above preferred process the raw material is monosodium salt of threonine, threonine or the monopotassium salt of threonine. The solubility of threonine can be enhanced by dissolving it in MOH (resulting in the formation of monosodium or monopotassium salt); having about 0.6-1.4 equivalents of base is preferred. In the manufacturing of THDA the monosodium salt or monopotassium salt of threonine is then dissolved in water and formaldehyde and cyanide are added to obtain final reaction mixture with acidic or neutral pH.
In the case of synthesis of the intermediate nitrile the addition of formaldehyde and hydrogen cyanide preferably takes place at a temperature between 0 and 70° C., preferably 0 and 40° C. The result is an intermediate product having two nitrile functionalities. These types of products are known as aminoacetonitriles or, for short, “nitriles”. The nitrile of THDA, e.g. threonine-N,N-diacetonitrile, is also indicated as THDN below. The nitrile, being a water-soluble compound, is hydrolyzed in a second step applying caustic.
The overall reaction will be:
CH3—CHOH—C(H)(COOM′)-N—(CH2—CN)2+2M(OH)+2H2O→CH3—CHOH—C(H)(COOM′)-N—(CH2—COOM)2+2NH3
(aminoacetonitrile intermediate+base→aminocarboxylate+ammonia)
In the above reaction each M and M′ may be the same or different and represent an alkali metal ion.
The process has as an additional benefit that having potassium THDN one needs only sodium hydroxide to produce the THDA-KNa2. Not all production locations have access to KOH or storage tanks of KOH; NaOH is more commonly used. Production of a mixed salt is easier than of the full potassium version that requires KOH to be present in each location, i.e. the location carrying out the nitrile hydrolysis only needs the commonly used NaOH.
Accordingly, a process is provided wherein in the first step the threonine diacetonitrile monopotassium salt is formed by reacting either potassium salt of threonine with hydrogen cyanide and formaldehyde or threonine with potassium cyanide and formaldehyde, the nitrile being hydrolyzed with sodium hydroxide in the subsequent step.
As starting material instead of threonine also the potassium salt thereof can be employed. The main advantage of monopotassium salt of threonine in the production process is its very high solubility even at room temperature. Monosodium threonine has a high solubility in water at room temperature (higher solubility compared to the non-salt threonine itself), monopotassium threonine has an even higher solubility. The more concentrated the threonine can be processed, the less water removal is required to make a concentrated THDA solution. The monosodium THDN (=threonine diacetonitrile monosodium salt) manufactured has a concentration related to the maximum achievable concentration of the monosodium salt of threonine and the amount of water added by using aqueous formaldehyde. It will be clear that the use of concentrated formaldehyde solutions is advantageous.
In the case of the potassium version of THDN, the final nitrile concentration will be higher due to the higher solubility of potassium salt of threonine. It allows for more economical transport, more output per reactor volume, lower energy costs, and is an easy way to produce highly concentrated final THDA solutions in the hydrolysis of the nitrile functionalities without water removal.
To be able to make specific NaxKyHzTHDA salts of the invention, a process wherein the ratio between x and y can be easily fine-tuned is also desired.
Therefore the invention provides the following two alternative processes. Firstly, a process comprising titrating threonine-N,N-diacetic acid (or an appropriate derivative or salt thereof) with a sodium salt and a potassium salt wherein the molar ratio of sodium to potassium in the materials is between 5:1 and 1:1 and, secondly, a process of mixing the trisodium salt of THDA and the tripotassium salt of THDA in a molar ratio of between 5:1 and 1:1.
The complexes of the present invention are made by contacting a salt of threonine diacetic acid or the acidic version of threonine diacetic acid with a compound containing a divalent or trivalent metal cation, like a salt of such a metal cation, preferably, the carbonate, oxide or hydroxide salt of such cation to avoid the formation of further salts, even more preferably the oxide salt, as hydroxide salts sometimes are not too soluble and the use of carbonate salts may result in the formation of a considerable amount of CO2 gas, which is sometimes undesirable. When using a metal oxide, it is preferred to use the threonine N—N-diacetic acid in the acidic version. The complexes are normally made in a solvent, preferably water.
The ammonium salts of the present invention are preferably made by contacting the acidic version of threonine diacetic acid (i.e. wherein at least one of the counterions is a hydrogen ion) with an ammonium salt or ammonia, preferably with NH4OH.
Finally, the present invention relates to the use of the alkali metal salts in a detergent or bleaching composition, a descaling composition, a microbial composition, human food or animal feed composition, an oil or gas well treatment composition, a micronutrient composition, in gas sweetening, pulp and paper bleaching, drilling, or in the preparation of any of such compositions.
EXAMPLES Example 1 The Synthesis of Trisodium Threonine Diacetate Using Sodium Cyanide
A 1 liter reactor was charged with 178.5 g threonine, (1.5 moles), 300 g water, and 130 g 50 wt % aqueous NaOH (1.6 moles). The reactor contents were heated to boiling temperature. Simultaneously in circa 3 hours 4.0 moles sodium cyanide solution (30 wt %) and 4.0 moles formaldehyde solution (44 wt %) were dosed. After the dosing was completed 2 hrs of boiling off ammonia/water took place (level control of the mixture by addition of water).
Circa 995 grams of a light-coloured solution having a Fe-sequestering capacity of 48 wt % were obtained, which contained <1 wt % of the starting material, threonine, indicating a good conversion.
13C and 1H NMR showed threonine diacetate formation.
Example 2 The Synthesis of Trisodium Threonine Diacetate Using HCN
A 1 liter reactor equipped with a stirrer, thermometer, and pH meter was charged with 104 g threonine (0.87 moles), 500 g water, and 5.5 grams 50 wt % aqueous NaOH. To this solution 67 g 44.3% formaldehyde solution (0.99 moles) were added. Subsequently over a period of 80 minutes, 54 g HCN (2.00) moles and 67 g (0.99 moles) 44.3 wt % formaldehyde were co-dosed. The pH was adjusted to 4 with 50% sodium hydroxide. The threonine diacetonitrile solution was dosed over a period of 90 minutes to a reactor that contained 209 g 50% caustic and 250 g water. After dosing had been completed the ammonia was boiled off by evaporating water/ammonia at 109° C. using level control by addition of water. The reactor mixture (650 grams) showed a Fe-sequestering capacity of 28%.
1H and 13C NMR analysis was used to prove that threonine diacetate was formed.
Example 3 The Synthesis of Trisodium Threonine Diacetate Using Monochloroacetic Acid
A 3 liter jacketed reactor with baffles and turbine stirrer was charged with 858 g of water and 361.0 g (3 moles) of L-threonine (99%, Fluka). This slurry is heated to 60° C. The dosing of 50 wt % aqueous NaOH solution was started and the pH value was maintained at 8.0 during the process when dosing a 42.9 wt % aqueous solution of sodium monochloroacetate. The reaction was monitored by the determination of its sequestering value.
A constant sequestering value having been reached, a total of 2,584.4 g (9.52 moles) of a 42.9% aqueous solution of sodium monochloroacetate and 788 g (9.85 moles) of a 50% aqueous NaOH solution was dosed altogether.
The formation of the desired product could be proven by NMR- and CZE-analytical techniques.
Example 4 The Synthesis of Threonine Diacetic Acid
The solution obtained in example 1 was acidified using an ion exchange resin. Acidification took place using Amberlite IR-120, a strong acid ion exchange resin: 55 g of GLDA solution, 110 g of Amberlite IR-120 as such, and ca 100 g of water were stirred in a 500 ml round-bottomed flask for at least 48 h. After filtering off the resin the solution was dried by evaporation of water at reduced pressure at 70° C. The light-coloured crispy foam obtained was further dried in a vacuum oven at 65° C. This resulted in a solid product in a yield of circa 85%.
NMR and FT-IR showed THDA:THDAring closed in a weight ratio of 90:10. This means that the THDA acid was formed but during the formation part of it cyclized and this created the product as further described in Example 5 below.
Example 5 The synthesis of (2R,3S)-4-(carboxymethyl)-2-methyl-6-oxomorpholine-3-carboxylic acid
The ratio of open/closed structure in solution is dependent on a number of factors such as e.g. pH-value, concentration. The ratio of open/closed structure in solid form strongly depends on factors like e.g. drying time, temperature, strength of vacuum applied.
The product obtained in Example 4 was dried for 1 month at 40° C.; this resulted in a solid product having a ratio THDA:THDAring closed=10:90 proven by NMR and FT-IR.
Example 6 Acidification with Concentrated Hydrochloric Acid
To 25 g of the solution of Example 1 (pH=13.3) in a 250 ml round-bottomed flask carefully concentrated HCl was added dropwise. Water and surplus HCl were removed with a rotavap under reduced pressure at 100° C. until a crispy (crystalline) foam remained. This material was dried further in the 250 ml round-bottomed flask in a vacuum oven at 100° C. for 48 h.
NMR and FT-IR showed the THDA:THDAring closed ratio of 60:40.
Example 7 Acidification with Glacial Acetic Acid
Water was removed from 50.8 g of the solution of Example 1 using a rotavap at 65° C. under reduced pressure. This resulted in 39.41 g of solid material. After dissolving this solid in glacial acetic acid (100 ml) the solution was precipitated by mixing with about 1,200 ml of isopropyl alcohol (IPA). After filtration through a G2 filter frit the solid was dried in a vacuum oven under reduced pressure at 100° C., resulting in 15.49 g of colourless material with a THDA:THDAring closed ratio of 80:20
Example 8 The Synthesis of Threonine Diacetate Solid
The solution obtained in Example 1 was used to prepare the powder of threonine diacetate.
In spite of the hygroscopic nature of THDA-Na3 solid, the solution was easy to spray-dry using an inlet air temperature of 200° C. and tuning the outlet temperature at 115° C. by the flow rate. A free flowing crystalline white powder was obtained. The moisture content of ca. 7% was determined by Karl Fisher titration.
Example 9 The Synthesis of Calcium Complex of Threonine
The pH of 37.8 wt % aqueous solution of THDA-Na3 was adjusted to pH=6 by addition of 37 wt % aqueous HCl. To the obtained mixture an equimolar amount of an aqueous solution of CaCl2.2H2O was added, followed by partial evaporation under vacuum to give a concentrated mixture. The concentrated mixture was left standing overnight at room temperature for further crystallization. The obtained solids were filtered off, washed with water (3×1 ml), and dried under vacuum (50° C.) to obtain white crystals. The formation of the crystalline Ca-THDA complex was supported by XRD, ICP, ESI-MS, and NMR analysis of the isolated material.
Example 10 The Synthesis of Iron (III) Complex of Threonine Diacetate
33.4 wt % THDA.Na3 (2 g, 2.2 mM; prepared by adjusting pH of 38 wt % THDA.Na3 to 7 with 70 wt % HClO4) was added to a solution of Fe(ClO4)3.xH2O (1.242 g, 2.2 mM, determined by potentiometric titration) in water (0.62 ml). Water (0.95 g) was partially evaporated from the reaction mixture under vacuum to give a yellow-brown transparent viscous solution. The concentrated solution was left to crystallize at ambient temperature for 2 h. The solids were filtered off, washed with water (0.5 ml), and dried under vacuum (50° C.) to obtain 0.681 g of a yellow crystalline powder. The iron complex formation was supported by XRD, ICP and NMR data.
Example 11 The Synthesis of Zinc Complex of Threonine Diacetate
The pH of 37.8 wt % aqueous solution of THDA-Na3 (10 g, 12.7 mM) was adjusted to pH=7 by addition of 37 wt % aqueous HCl. To the obtained mixture a solution of ZnCl2 (1.719 g, 12.7 mM) in water (3.0 g) was added, followed by partial evaporation under vacuum to give 11.8 g of concentrated mixture containing white solids. The solids were filtered off, washed with water (3.4 ml), and dried under vacuum (50° C.) to obtain 2.34 g of white crystals. The formation of the crystalline Zn-THDA complex was supported by XRD, ICP, ESI-MS, and NMR analysis of the isolated material.
Example 12 The Synthesis of Copper(II) Complex of Threonine Diacetate
A 34.3 wt % solution of THDA.Na3 in water (2 g, 2.3 mM; prepared by adjusting pH of 38 wt % THDA.Na3 to 7 with 37 wt % HCl) was added to a solution of anhydrous CuCl2 (0.306 g, 2.3 mM) in water (1 ml). The resulting blue homogeneous solution was partially evaporated (1.42 g of water was removed) under vacuum and left at ambient temperature for crystallization. After 5 days at room temperature the crystals were filtered off, washed with water (0.5 ml), and dried under vacuum (50° C.) to obtain 0.37 g of blue crystals. The formation of the expected crystalline Cu-THDA complex was supported by XRD, ICP, ESI-MS, and NMR analysis of the isolated material.
Example 13 Use of THDA in Several Applications to Sequester Calcium or Iron
a) Use of THDA for Dissolving Insoluble Calcium Salts
A mixture of CaCO3 (1.26 g, 12.6 mM), 37.8 wt % THDA.Na3 in water (15 g, 18.8 mM), and water (45 g) was vigorously stirred for 6 h. The experiment was performed at room temperature and at 50° C. Samples (1 ml) were taken from the mixture every 0.5 h and filtered through a 0.45 μm filter. The concentration of calcium in the filtered samples was determined using the ICP method. It was shown that a significant amount of CaCO3 could be dissolved. The dissolution occurred noticeably faster at 50° C.
b) Use of THDA for Sequestering Fe(III) at Low and High pH.
Potentiometric titration of THDA with FeCl3 at pH 3-4 and 11.5 gave the iron total sequestering values (Fe-TSV) of 37.8 and 27.8%, respectively. This demonstrated that even at high pH a significant amount of Fe(III) is bound by the chelating agent. All Fe(III) is bound by THDA at pH 3-4.
Comparative Example 14 Preparation of serine-N,N-diacetic acid using sodium cyanide
Following the procedure as in Example 1, a 1 liter reactor was charged with 157.6 g serine, (1.5 moles), 120 g water, and 123 g 50 wt % aqueous NaOH (1.54 moles). The reactor contents were heated to boiling temperature. Simultaneously in circa 3 hours 4.0 moles sodium cyanide solution (30 wt %) and 4.0 moles formaldehyde solution (44 wt %) were dosed. After the dosing was completed 2 hrs of boiling off ammonia/water took place (level control of the mixture by addition of water). Ca. 1080 grams of a black-brown solution having a Fe-sequestering capacity of 40 wt % were obtained, which contained <1 wt % of the starting material, serine, indicating a good conversion. 13C and 1H NMR showed serine diacetate formation.
Example 15 Cyclisation of threonine diacetic acid to (2R,3S)-4-(carboxymethyl)-2-methyl-6-oxomorpholine-3-carboxylic acid
A 30% aqueous solution of disodium threonine diacetate (129 mg) was mixed well with a DMSO-d6/TFA solution (2761 mg, 80:20 w/w) and changes in the obtained mixture were monitored by 1H NMR at ambient temperature. The steady state was reached after 40 minutes with a conversion of 90% of THDA to cyclic-THDA.
Comparative Example 16 Cyclisation of serine diacetic acid to (S)-4-(carboxymethyl)-6-oxomorpholine-3-carboxylic acid
A 30% aqueous solution of disodium serine diacetate (136 mg) was mixed well with a DMSO-d6/TFA solution (2911 mg, 80:20 w/w) and changes in the obtained mixture were monitored by 1H NMR at ambient temperature. The steady state was reached after 100 minutes with a conversion of 43% of SerDA to cyclic-SerDA. The above experiments support that THDA can be used in applications that relate to dissolving carbonate or sequestering iron, such as use in the oil field (e.g. dissolving CaCO3 and controlling iron in subterranean treatment), use in a feed, food or micronutrient composition (e.g. complexing iron and calcium for delivery to growing substrates), use in detergents and water treatments (e.g. sequestering calcium from water to soften water and sequestering iron present in stains), and many more uses.

Claims (12)

The invention claimed is:
1. A process to prepare threonine-N,N-diacetic acid or a salt thereof comprising two or more steps wherein in a first step threonine, a sodium or potassium salt thereof or a mixture thereof is reacted with formaldehyde and hydrogen cyanide, at a pH equal to or below 7 to form a nitrile compound, and in a second step the nitrile compound formed in the first step is hydrolyzed by the addition of an acid or base.
2. A process to prepare threonine-N,N-diacetic acid or a salt thereof comprising reacting threonine, a sodium or potassium salt thereof or a mixture thereof with formaldehyde, hydrogen cyanide, a potassium or sodium salt thereof or a mixture thereof, and potassium hydroxide, sodium hydroxide or a mixture thereof, in an aqueous solution at an alkaline pH and at an elevated temperature to remove formed NH3.
3. A process to prepare threonine-N,N-diacetic acid or a salt thereof, wherein threonine is reacted with a monohaloacetic acid at a temperature of 20 to 80° C. and an alkaline pH.
4. The process of claim 1 wherein said nitrile compound is threonine-N,N-diacetonitrile or a salt thereof.
5. The process of claim 1 wherein subsequent to the hydrolysis step an acidification step is performed.
6. The process of claim 2 wherein subsequent to the reaction at alkaline pH an acidification step is performed.
7. The process of claim 3 wherein said monohaloacetic acid is monochloroacetic acid.
8. The process of claim 3 wherein the reaction product is a salt of threonine-N,N-diacetic acid and a subsequent acidification step is performed to convert the salt formed into the acid.
9. A composition comprising a compound selected from the group consisting of
a complex of threonine-N,N-diacetic acid and a divalent or trivalent cation, wherein the cation is selected from the group of calcium, magnesium, iron, zinc, manganese, aluminium, copper, and cobalt; and
a salt of threonine-N,N-diacetic acid of the formula CH3—CHOH—C(H)(COOM)-N—(CH2—COOM)2, wherein at least one M is chosen from the group of sodium, potassium, lithium, cesium, and ammonium.
10. The composition of claim 9 wherein said compound is in crystalline form.
11. The composition of claim 9 wherein said composition is a formulation comprising a liquid.
12. The composition of claim 11 wherein the liquid is water.
US14/905,432 2013-07-16 2014-07-11 Salts, crystals, complexes, and derivatives of threonine diacetic acid, a process to prepare threonine diacetic acid, and the use thereof Active US9416095B2 (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EP13176649 2013-07-16
EP13176649.5 2013-07-16
EP13176649 2013-07-16
PCT/EP2014/064894 WO2015007630A1 (en) 2013-07-16 2014-07-11 New salts, crystals, complexes, and derivatives of threonine diacetic acid, a process to prepare threonine diacetic acid, and the use thereof

Publications (2)

Publication Number Publication Date
US20160159730A1 US20160159730A1 (en) 2016-06-09
US9416095B2 true US9416095B2 (en) 2016-08-16

Family

ID=48783129

Family Applications (1)

Application Number Title Priority Date Filing Date
US14/905,432 Active US9416095B2 (en) 2013-07-16 2014-07-11 Salts, crystals, complexes, and derivatives of threonine diacetic acid, a process to prepare threonine diacetic acid, and the use thereof

Country Status (5)

Country Link
US (1) US9416095B2 (en)
EP (1) EP3022171B1 (en)
CN (1) CN105377809B (en)
CA (1) CA2917252A1 (en)
WO (1) WO2015007630A1 (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104761462B (en) * 2015-03-23 2017-03-15 长沙兴嘉生物工程股份有限公司 A kind of preparation method of copper-threonine
RU2706358C2 (en) 2015-05-13 2019-11-18 Басф Се Method of producing mixtures of chelating agents
CN109912440A (en) * 2018-11-23 2019-06-21 南京华狮新材料有限公司 Amino acid type chelated dose of one kind and its method for making in scale and application
CN110903206A (en) * 2019-12-20 2020-03-24 上海永通生态工程股份有限公司 Zinc methylglycine diacetate, manganese methylglycine diacetate and preparation method thereof

Citations (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5019296A (en) 1987-04-11 1991-05-28 Basf Aktiengesellschaft Serine-N,N-diacetic acid and derivatives as complexing agents and detergents containing same
EP0599620A1 (en) 1992-11-25 1994-06-01 Konica Corporation Chemical compositions and a processing method using the same for processing silver halide photographic light-sensitive material
EP0624821A1 (en) 1993-05-10 1994-11-17 Konica Corporation Tablet for processing silver halide color photographic light-sensitive materials
US5521056A (en) 1995-01-10 1996-05-28 Eastman Kodak Company Photographic peracid bleaching composition and processing method using ternary iron carboxylate complexes as catalysts in peracid bleaching solutions
EP0723194A1 (en) 1995-01-10 1996-07-24 Eastman Kodak Company Photographic bleaching compositions and processing method using ternary iron carboxylate complexes as bleaching agents
JPH1121584A (en) 1997-07-03 1999-01-26 Kao Corp Detergent composition
JPH1121585A (en) 1997-07-03 1999-01-26 Kao Corp Detergent composition
JPH1192436A (en) 1997-09-22 1999-04-06 Kao Corp Amidoaminocarboxylic acid or salt thereof, and detergent composition by using the same
JP2000008081A (en) 1998-06-25 2000-01-11 Kao Corp Detergent composition
JP2000026890A (en) 1998-07-06 2000-01-25 Kao Corp Detergent composition
EP1004571A1 (en) 1998-05-27 2000-05-31 Showa Denko Kabushiki Kaisha Processes for producing amino acid having secondary or tertiary amino group and three or more carboxyl groups and its salt
JP2001342453A (en) 2000-06-01 2001-12-14 Mitsubishi Rayon Co Ltd Chelating agent composition
JP2002020792A (en) 2000-07-10 2002-01-23 Kao Corp Detergent composition
JP2002287307A (en) 2001-03-23 2002-10-03 Konica Corp Solid processing agent for silver halide photographic sensitive material
JP2002296745A (en) 2001-03-30 2002-10-09 Konica Corp Bleaching solution for silver halide color photographic sensitive material and processing method using the same
WO2003022406A1 (en) 2001-09-12 2003-03-20 Basf Aktiengesellschaft Method for desulphurising acid gases using catalysts that are insensitive to oxidation and contain aminocarboxylate
JP2004204055A (en) 2002-12-25 2004-07-22 Adeka Clean Aid Co Ltd Cleanser composition
WO2005095673A1 (en) 2004-03-25 2005-10-13 Dr.-Ing. Max Schlötter Gmbh & Co. Kg Stripping solution and use thereof
JP2009218473A (en) 2008-03-12 2009-09-24 Fujifilm Corp Cleaning agent and method of washing semiconductor device using the same
US20110257431A1 (en) 2010-03-18 2011-10-20 Basf Se Process for producing side product-free aminocarboxylates
EP2388308A1 (en) 2010-05-19 2011-11-23 Dequest AG Cleaning composition with improved stain removal
WO2011144699A1 (en) 2010-05-19 2011-11-24 Dequest Ag Cleaning composition with improved stain removal
WO2011154875A1 (en) 2010-06-09 2011-12-15 Basf Se Aqueous alkaline etching and cleaning composition and method for treating the surface of silicon substrates
EP2086923B1 (en) 2006-11-30 2012-08-15 Akzo Nobel N.V. Process to prepare amino acid-n, n-diacetic acid compounds

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4211713A1 (en) * 1992-04-08 1993-10-14 Basf Ag New amino di:carboxylic-N,N-di:acetic acid deriv., useful as complexing agents - is prepd. from amino di:carboxylic acids, formaldehyde and hydrocyanic acid, or alkali metal cyanide, with amino di:carboxylic acid-N,N-di:acetonitrile as intermediate
CA2717180C (en) * 2008-03-03 2016-09-13 Basf Se Method for the production of aminodicarboxylic acid-n,n-diacetic acids
US8501988B2 (en) * 2008-04-17 2013-08-06 Ecolab Usa Inc. Synthesis and applications of amino carboxylates

Patent Citations (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5019296A (en) 1987-04-11 1991-05-28 Basf Aktiengesellschaft Serine-N,N-diacetic acid and derivatives as complexing agents and detergents containing same
EP0599620A1 (en) 1992-11-25 1994-06-01 Konica Corporation Chemical compositions and a processing method using the same for processing silver halide photographic light-sensitive material
EP0624821A1 (en) 1993-05-10 1994-11-17 Konica Corporation Tablet for processing silver halide color photographic light-sensitive materials
US5521056A (en) 1995-01-10 1996-05-28 Eastman Kodak Company Photographic peracid bleaching composition and processing method using ternary iron carboxylate complexes as catalysts in peracid bleaching solutions
EP0723194A1 (en) 1995-01-10 1996-07-24 Eastman Kodak Company Photographic bleaching compositions and processing method using ternary iron carboxylate complexes as bleaching agents
JPH1121584A (en) 1997-07-03 1999-01-26 Kao Corp Detergent composition
JPH1121585A (en) 1997-07-03 1999-01-26 Kao Corp Detergent composition
JPH1192436A (en) 1997-09-22 1999-04-06 Kao Corp Amidoaminocarboxylic acid or salt thereof, and detergent composition by using the same
EP1004571A1 (en) 1998-05-27 2000-05-31 Showa Denko Kabushiki Kaisha Processes for producing amino acid having secondary or tertiary amino group and three or more carboxyl groups and its salt
JP2000008081A (en) 1998-06-25 2000-01-11 Kao Corp Detergent composition
JP2000026890A (en) 1998-07-06 2000-01-25 Kao Corp Detergent composition
JP2001342453A (en) 2000-06-01 2001-12-14 Mitsubishi Rayon Co Ltd Chelating agent composition
JP2002020792A (en) 2000-07-10 2002-01-23 Kao Corp Detergent composition
JP2002287307A (en) 2001-03-23 2002-10-03 Konica Corp Solid processing agent for silver halide photographic sensitive material
JP2002296745A (en) 2001-03-30 2002-10-09 Konica Corp Bleaching solution for silver halide color photographic sensitive material and processing method using the same
WO2003022406A1 (en) 2001-09-12 2003-03-20 Basf Aktiengesellschaft Method for desulphurising acid gases using catalysts that are insensitive to oxidation and contain aminocarboxylate
JP2004204055A (en) 2002-12-25 2004-07-22 Adeka Clean Aid Co Ltd Cleanser composition
WO2005095673A1 (en) 2004-03-25 2005-10-13 Dr.-Ing. Max Schlötter Gmbh & Co. Kg Stripping solution and use thereof
EP2086923B1 (en) 2006-11-30 2012-08-15 Akzo Nobel N.V. Process to prepare amino acid-n, n-diacetic acid compounds
JP2009218473A (en) 2008-03-12 2009-09-24 Fujifilm Corp Cleaning agent and method of washing semiconductor device using the same
US20110257431A1 (en) 2010-03-18 2011-10-20 Basf Se Process for producing side product-free aminocarboxylates
EP2388308A1 (en) 2010-05-19 2011-11-23 Dequest AG Cleaning composition with improved stain removal
WO2011144699A1 (en) 2010-05-19 2011-11-24 Dequest Ag Cleaning composition with improved stain removal
WO2011154875A1 (en) 2010-06-09 2011-12-15 Basf Se Aqueous alkaline etching and cleaning composition and method for treating the surface of silicon substrates

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
European Search Report for EP 13176649.5, date Nov. 25, 2013.

Also Published As

Publication number Publication date
CN105377809A (en) 2016-03-02
CA2917252A1 (en) 2015-01-22
CN105377809B (en) 2018-06-08
US20160159730A1 (en) 2016-06-09
WO2015007630A1 (en) 2015-01-22
EP3022171B1 (en) 2017-07-05
EP3022171A1 (en) 2016-05-25

Similar Documents

Publication Publication Date Title
CA2696669C (en) Alkali metal salt of glutamic acid n,n-diacetic acid, a process to prepare such salt, and the use thereof
US9416095B2 (en) Salts, crystals, complexes, and derivatives of threonine diacetic acid, a process to prepare threonine diacetic acid, and the use thereof
JP6087317B2 (en) Phosphonate compounds
JP2012527426A5 (en)
JP4430326B2 (en) Method for producing ammonium iminodisuccinate metal salt and ammonium iminodisuccinate metal salt
JPH06172291A (en) N,n&#39;-diacetic acid n&#39;-cyanomethyl, its salt and their production
US4116991A (en) Hydroxy-containing agents for chelating metal ions and a process for preparing same
CN111606818A (en) Chelating agent, cleaning agent and preparation method of chelating agent
WO2021226845A1 (en) Chelating agent, cleaning agent, and method for preparing chelating agent
US20210403412A1 (en) Production of nitrogen-containing chelators
WO2009071630A2 (en) A composition and a manufacturing method thereof
JPH09194448A (en) Production of diamine-type polyamino acid by connection of bimolecular amino acid and biodegradable chelating agent containing the same
US20230382846A1 (en) Method of forming a chelating composition
US20090145189A1 (en) Composition and a manufacturing method thereof
CN114989029A (en) Chelating agent, cleaning agent and preparation method of chelating agent
CN117142970A (en) Method of forming a chelating composition
JP4423733B2 (en) Aminopolycarboxylate, process for its production and use thereof
JP2007084516A (en) Cyclobutanamide compound, method for producing the same and chelating agent
RU2489420C1 (en) Method of producing ethylenediamine-n-monopropionic acid
JP2004359700A (en) PRODUCTION OF beta-ALANINE-N,N-DIACETIC ACID AND ITS SALT
JP2002193902A (en) Dialkylethylenediaminedimalonic acids, and their production method and use
JPH0324465B2 (en)
JP2008063338A (en) Process for producing n-carboxyalkyl-amino acid
JP2008247811A (en) Method for synthesizing low-ammonium type titanium peroxo compound

Legal Events

Date Code Title Description
AS Assignment

Owner name: AKZO NOBEL CHEMICALS INTERNATIONAL B.V., NETHERLAN

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:CARSTENS, AXEL;BOONSTRA, TJERK OEDSE;ZAITSEV, ALEXEY BORISOVICH;AND OTHERS;SIGNING DATES FROM 20151028 TO 20151103;REEL/FRAME:037500/0170

STCF Information on status: patent grant

Free format text: PATENTED CASE

AS Assignment

Owner name: WILMINGTON TRUST (LONDON) LIMITED, AS COLLATERAL AGENT, ENGLAND

Free format text: SECURITY INTEREST;ASSIGNORS:STARFRUIT US MERGER SUB 1 LLC;STARFRUIT US MERGER SUB 2 LLC;AKZO NOBEL SURFACE CHEMISTRY LLC;AND OTHERS;REEL/FRAME:047231/0001

Effective date: 20181001

Owner name: WILMINGTON TRUST (LONDON) LIMITED, AS COLLATERAL A

Free format text: SECURITY INTEREST;ASSIGNORS:STARFRUIT US MERGER SUB 1 LLC;STARFRUIT US MERGER SUB 2 LLC;AKZO NOBEL SURFACE CHEMISTRY LLC;AND OTHERS;REEL/FRAME:047231/0001

Effective date: 20181001

AS Assignment

Owner name: NOURYON CHEMICALS INTERNATIONAL B.V., NETHERLANDS

Free format text: CHANGE OF NAME;ASSIGNOR:AKZO NOBEL CHEMICALS INTERNATIONAL B.V.;REEL/FRAME:050426/0671

Effective date: 20190601

MAFP Maintenance fee payment

Free format text: PAYMENT OF MAINTENANCE FEE, 4TH YEAR, LARGE ENTITY (ORIGINAL EVENT CODE: M1551); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY

Year of fee payment: 4

MAFP Maintenance fee payment

Free format text: PAYMENT OF MAINTENANCE FEE, 8TH YEAR, LARGE ENTITY (ORIGINAL EVENT CODE: M1552); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY

Year of fee payment: 8